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EP3904295A1 - Herstellungsverfahren für lithium enthaltendes komplexoxid - Google Patents

Herstellungsverfahren für lithium enthaltendes komplexoxid Download PDF

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Publication number
EP3904295A1
EP3904295A1 EP19902289.8A EP19902289A EP3904295A1 EP 3904295 A1 EP3904295 A1 EP 3904295A1 EP 19902289 A EP19902289 A EP 19902289A EP 3904295 A1 EP3904295 A1 EP 3904295A1
Authority
EP
European Patent Office
Prior art keywords
lithium
composite oxide
hydroxide
metal
nickel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19902289.8A
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English (en)
French (fr)
Other versions
EP3904295A4 (de
Inventor
Daisuke Katou
Tomoo Takayama
Takuya JIN
Mitsuru Iwai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Intellectual Property Management Co Ltd
Original Assignee
Panasonic Intellectual Property Management Co Ltd
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Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Publication of EP3904295A1 publication Critical patent/EP3904295A1/de
Publication of EP3904295A4 publication Critical patent/EP3904295A4/de
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a method for producing a lithium-containing composite oxide.
  • a secondary battery represented by a lithium ion secondary battery includes a positive electrode, a negative electrode, and an electrolyte.
  • the positive electrode includes a lithium-containing composite oxide serving as a positive electrode active material.
  • the lithium-containing composite oxide for example, lithium nickelate is used which is advantageous in achieving a higher capacity, and with an aim of further improving the battery characteristics, studies have been made to replace part of the nickel with a different kind of metal.
  • Patent Literature 1 relating to a method for producing a lithium-containing composite oxide, discloses molding a mixture of a lithium compound and a hydroxide containing one or more other metals, such as nickel and cobalt, and packing the resultant molded body into a reaction vessel, followed by baking while an oxidizing gas is forced to pass therethrough.
  • Patent Literature 1 a large amount of water may be produced during baking from the molded body including a hydroxide containing nickel and the like, which may cause the molded body to collapse.
  • the molded body collapses less dense portions increase, which may result in an insufficient particle-to-particle contact in the molded body, leading to a reduced heat conductivity of the molded body and thus to a reduced crystallinity of the baked body.
  • the difference between the less dense portions and the dense portions i.e., the variation in the degree of particle-to-particle contact in the molded body
  • the variation in the degree of baking increases, which may cause the baked body to be non-homogeneous.
  • one aspect of the present disclosure relates to a method for producing a lithium-containing composite oxide, the method including: a first step of preparing a lithium hydroxide; a second step of heating a hydroxide containing nickel and a metal M1 other than lithium and nickel to 300 °C or higher and 800 °C or lower, to obtain a composite oxide containing the nickel and the metal M1; a third step of mixing the lithium hydroxide and the composite oxide, to obtain a mixture; a fourth step of compression-molding the mixture, to obtain a molded body; and a fifth step of baking the molded body at 600 °C or higher and 850 °C or lower, to obtain a baked body.
  • a homogeneous lithium-containing composite oxide having high crystallinity can be provided.
  • FIG. 1 A partially cut-away schematic oblique view of a secondary battery including, as a positive electrode active material, a lithium-containing composite oxide obtained by the production method according to an embodiment of the present disclosure.
  • a method for producing a lithium-containing composite oxide according to the present disclosure includes: a first step of preparing a lithium hydroxide; a second step of heating a hydroxide (hereinafter, sometimes referred to as a hydroxide A) containing nickel and a metal M1 other than lithium and nickel to 300 °C or higher and 800 °C or lower, to obtain a composite oxide (hereinafter, sometimes referred to as a composite oxide B) containing the nickel and the metal M1; a third step of mixing the lithium hydroxide and the aforementioned composite oxide, to obtain a mixture; a fourth step of compression-molding the mixture, to obtain a molded body; and a fifth step of baking the molded body at 600 °C or higher and 850 °C or lower, to obtain a baked body (lithium-containing composite oxide).
  • a hydroxide hereinafter, sometimes referred to as a hydroxide A
  • a composite oxide hereinafter, sometimes referred to as a composite oxide B
  • the composite oxide B obtained by subjecting the hydroxide A to a heat treatment as a material of the molded body, the generation of water during baking from the molded body can be suppressed, and the collapse of the molded body can be suppressed.
  • the decrease in the degree of contact between the lithium hydroxide and the composite oxide B, as well as the decrease in the heat conductivity of the molded body, due to the collapse of the molded body can be suppressed.
  • This can improve the reactivity between the lithium hydroxide and the composite oxide B, which can improve the crystallinity of the baked body (lithium-containing composite oxide).
  • a lithium-containing composite oxide having a large crystallite size can be obtained.
  • the increase in the variation in the degree of baking can be suppressed by the suppression of the collapse of the molded body, and thus, a homogeneous baked body (lithium-containing composite oxide) with small variation in the crystallite size can be provided.
  • the crystallite size of the lithium-containing composite oxide can be considerably increased to, for example, about 160 nm.
  • a favorable contact between the lithium hydroxide and the composite oxide B is considered to have been maintained due to less production of water during baking, which is combined with the excellent heat conductivity of the molded body including these two compounds, resulting in specific improvement in the reactivity between the two compounds.
  • the crystallite size of the lithium-containing composite oxide can be determined by the following method.
  • the lithium-containing composite oxide is subjected to X-ray diffractometry (XRD), to give an X-ray diffraction pattern thereof.
  • XRD X-ray diffractometry
  • WPPF whole-powder-pattern fitting
  • the composite oxide B By using the composite oxide B, the atomic ratio of the nickel to the metal M1 (e.g., Co, Al) can be easily controlled, and a homogeneous mixture tends to be obtained in the third step. Furthermore, the variation in the nickel-to-Ml atomic ratio among a plurality of the molded bodies can reduced, and a lithium-containing composite oxide having a target composition can be produced stably.
  • the metal M1 e.g., Co, Al
  • a powder of lithium hydroxide is prepared.
  • the average particle diameter (D50) of the lithium hydroxide is, for example, 10 ⁇ m or more and 500 ⁇ m or less.
  • the lithium hydroxide is highly reactive with the composite oxide B, and is advantageous in improving the crystallinity of the lithium-containing composite oxide.
  • the first step preferably includes a step (i) of heating the lithium hydroxide to dry.
  • the lithium hydroxide before dry may include a lithium hydroxide monohydrate.
  • the lithium hydroxide which is sufficiently dry, can be prepared. This can further suppress the release of water from the molded body during baking, which can further suppress the collapse of the molded body.
  • the heating temperature of the lithium hydroxide is preferably 100 °C or higher and equal to or lower than a melting point thereof.
  • the heating temperature is 100 °C or higher, the water contained in the lithium hydroxide can be efficiently removed.
  • the heating temperature is equal to or lower than the melting point, the particle form of the lithium hydroxide can be maintained, and the workability improves, making it easy to obtain a homogeneous mixture in the third step.
  • the heating time of the lithium hydroxide is, for example, 1 hour or longer and 10 hours or shorter.
  • the heating of the step (i) may be performed in air, but is preferably performed in a non-oxidizing atmosphere containing nitrogen, argon or the like.
  • the hydroxide A is heated to 300 °C or higher and 800 °C or lower, to give a composite oxide B.
  • the composite oxide B includes that in a state where the Ni site in the crystal lattice of a nickel oxide is partially replaced with the metal M1, or that in a state where the metal M1 is dissolved in solid in a nickel oxide.
  • the heating time of the hydroxide A is, for example, 30 minutes or longer and 10 hours or shorter.
  • the heating of the second step may be performed in a non-oxidizing atmosphere containing nitrogen or the like, and may be performed in an oxidizing atmosphere containing oxygen or the like.
  • the oxidizing atmosphere may be air, and may be an atmosphere having a higher oxygen partial pressure.
  • the oxygen concentration in the oxidizing atmosphere is, for example, 20% or more.
  • the hydroxide A preferably includes a composite hydroxide containing nickel and the metal M1.
  • the atomic ratio of the nickel to the metal M1 in the composite oxide B can be easily controlled, and a homogeneous mixture can be easily obtained in the third step. This makes it easy to uniformly disperse nickel and the metal M1 in the molded body, and thus to produce a lithium-containing composite oxide having a target composition.
  • the composite hydroxide can be produced by any known technique, such as a coprecipitation technique.
  • a coprecipitation technique an alkali is added to an aqueous solution containing a nickel salt and a salt of the metal M1, so that a composite hydroxide is coprecipitated.
  • the nickel salt may be, for example, nickel sulfate.
  • the salt of the metal M1 may be, for example, cobalt sulfate, aluminum sulfate, and the like.
  • the alkali may be, for example, sodium hydroxide.
  • the hydroxide A may include a nickel hydroxide and a hydroxide of the metal M1. Specifically, a nickel hydroxide and a hydroxide of the metal M1 may be prepared separately, and then mixed together to give a mixture, to which heat treatment may be applied, to form a composite oxide B.
  • Nickel is advantageous in achieving a higher capacity and reducing the cost.
  • the metal M1 preferably includes cobalt and a metal M2 other than cobalt. Cobalt is advantageous in extending the service life of the battery and other points.
  • the metal M2 preferably includes at least aluminum. Aluminum is advantageous in improving the thermal stability and other points. By using a lithium-containing composite oxide containing nickel, cobalt, and aluminum, as a positive electrode active material, a higher capacity and a longer service life of the secondary battery can be achieved.
  • the metal M2 may further include at least one selected from the group consisting of manganese, tungsten, niobium, magnesium, zirconium, and zinc.
  • the hydroxide A may include a nickel hydroxide, a cobalt hydroxide, and a hydroxide of the metal M2. Also, the hydroxide A may include a composite hydroxide containing two or more selected from the group consisting of nickel, cobalt, and the metal M2, and preferably includes a composite hydroxide containing nickel, cobalt, and the metal M2. When a composite hydroxide is used, nickel, cobalt, and the metal M2 can be easily uniformly dispersed in the molded body.
  • Ni:Co:M2 (1-x-y):x:y
  • x preferably satisfies 0.01 ⁇ x ⁇ 0.15
  • y preferably satisfies 0.001 ⁇ y ⁇ 0.1.
  • the effects produced by using nickel, cobalt, the metal M2 can be obtained in a balanced manner.
  • particles of the composite oxide B are preferably obtained by subjecting the particles of the composite hydroxide to heat treatment.
  • a homogeneous mixture can be efficiently obtained in the third step.
  • the composite hydroxide obtained by a coprecipitation technique can form secondary particles formed of aggregated primary particles.
  • the secondary particles of the composite hydroxide have an average particle diameter (D50) of, for example, 2 ⁇ m or more and 20 ⁇ m or less.
  • the average particle diameter (D50) of the secondary particles can be determined through particle size distribution measurement by laser diffractometry.
  • the average particle diameter (D50) is a median diameter at 50% cumulative volume in a volumetric particle size distribution.
  • the particle size of the composite oxide B may be adjusted by crushing and/or classifying at least one of the composite hydroxide and the composite oxide B, and may be adjusted by changing the conditions for preparing a composite hydroxide by a coprecipitation technique or the conditions for heat treatment of the second step.
  • the lithium hydroxide and the composite oxide B obtained in the second step are mixed together, to form a mixture.
  • the mixing of the third step is performed by a dry process.
  • the mixing of the lithium hydroxide and the composite oxide B is performed without adding a dispersion medium, such as water.
  • the mixture obtained in the third step is compression-molded, to give a molded body.
  • the compression molding of the fourth step is performed by a dry process.
  • the compression molding of the mixture is performed without adding a dispersion medium, such as water.
  • the molded body may be formed in any shape, but, in view of efficient and uniform application of heat thereto, is formed in, for example, a spherical shape, a spheroidal shape, a columnar shape, an elliptic columnar shape, a prismatic shape, or a disc shape.
  • the maximum diameter of the molded body is, for example, 1 mm or more and 50 mm or less.
  • a compression-molding machine such as a granulating machine, a pelleting machine, and a tableting machine, may be used.
  • the mixture is preferably compression-molded until the molded body has a density of 1.5 g/cm 3 or more and 2.2 g/cm 3 or less.
  • the density of the molded body is 1.5 g/cm 3 or more, the particles can be brought into sufficient contact (close contact) with each other, and the reaction between the particles tends to proceed smoothly, and also, the molded body is unlikely to collapse during baking.
  • the density of the molded body is 2.2 g/cm 3 or less, voids are formed in moderation within the molded body, and an oxidizing gas, such as oxygen, can be supplied also into the inside of the molded body, which can sufficiently reduce the variation in the degree of baking between the surface and the inside of the molded body.
  • the molded body obtained in the fourth step is baked at 600 °C or higher and 850 °C or lower, to obtain a baked body (lithium-containing composite oxide).
  • the baking time in the fifth step is, for example, 2 hours or longer and 30 hours or shorter.
  • the baking is usually performed in an oxidizing atmosphere containing oxygen or the like.
  • the oxidizing atmosphere may be air, and may be an atmosphere having a higher oxygen partial pressure.
  • the oxygen concentration in the oxidizing atmosphere is, for example, 20% or more.
  • the reactivity between the lithium hydroxide and the composite oxide B during baking can be improved, and a lithium-containing composite oxide with small lithium deficiency can be stably obtained.
  • the baking temperature and the baking time are within the ranges as above, the whole molded body can be efficiently and sufficiently baked.
  • the powder In the case of baking the mixture (powder) without subjecting it to compression-molding, the powder may be scattered as the oxidizing gas is supplied, or a molten material accumulated at the bottom of the reaction vessel during baking may prevent uniform baking.
  • the above inconvenience can be avoided.
  • the shape of the molded body can be retained during baking, and a baked body having almost the same shape as that of the molded body can be obtained.
  • a layered rock-salt type lithium-containing composite oxide in which nickel in the lithium nickelate is partially replaced with the metal M1 (cobalt and metal M2) can be obtained.
  • the lithium-containing composite oxide obtained in the fifth step preferably has a composition represented by a formula: Li a Ni 1-x-y Co x M2 y O 2 .
  • a satisfies 0.9 ⁇ a ⁇ 1.1
  • x satisfies 0.01 ⁇ x ⁇ 0.15
  • y satisfies 0.001 ⁇ y ⁇ 0.1.
  • the lithium hydroxide A composite hydroxide
  • the lithium hydroxide and the composite oxide B are mixed such that the atomic ratio: Li/(Ni+M1) of the lithium in the lithium hydroxide to the total of the nickel and the metal M1 in the composite oxide B exceeds 0.9 but is less than 1.1.
  • At least one of a step of crushing the baked body and a step of classifying the baked body may be included.
  • a ball mill, a mortar, and the like are used.
  • a sieve and the like are used.
  • the particle size of the lithium-containing composite oxide can be adjusted so that favorable negative electrode characteristics can be obtained.
  • the lithium-containing composite oxide can form secondary particle formed of aggregated primary particles.
  • the secondary particles of the lithium-containing composite oxide have an average particle diameter (D50) of, for example, 2 ⁇ m or more and 20 ⁇ m or less.
  • the lithium-containing composite oxide obtained by the above-described production method is preferably used as a positive electrode active material of a secondary battery. A description will be given below of the secondary battery.
  • the secondary battery includes a positive electrode including a positive electrode active material capable of electrochemically absorbing and releasing lithium ions, a negative electrode including a negative electrode active material capable of electrochemically absorbing and releasing lithium ions, and a non-aqueous electrolyte.
  • the positive electrode active material includes a lithium-containing composite oxide obtained by the above-described production method.
  • the positive electrode includes, for example, a positive electrode current collector, and a positive electrode material mixture layer formed on a surface of the positive electrode current collector.
  • the positive electrode material mixture layer may be formed on one surface or both surfaces of the positive electrode current collector.
  • the positive electrode material mixture essentially includes a positive electrode active material, and may optionally include a binder, an electrically conductive agent, and the like.
  • the positive electrode current collector may be made of, for example, stainless steel, aluminum, an aluminum alloy, and titanium.
  • the binder include polytetrafluoroethylene and polyvinylidene fluoride.
  • the conductive agent include: graphite, such as natural graphite and artificial graphite; and carbon blacks, such as the acetylene black.
  • the negative electrode includes, for example, a negative electrode current collector, and a negative electrode material mixture layer formed on a surface of the negative electrode current collector.
  • the negative electrode material mixture layer may be formed on one surface or both surfaces of the negative electrode current collector.
  • the negative electrode material mixture essentially includes a negative electrode active material, and may optionally include a binder, a thickener, and the like. Examples of the binder are as those exemplified for the positive electrode. Examples of the thickener include carboxymethyl cellulose (CMC) and modified products thereof (including salts such as Na salts).
  • the negative electrode current collector may be made of, for example, stainless steel, nickel, a nickel alloy, copper, and a copper alloy.
  • Examples of the negative electrode active material include: a carbon material; silicon; a silicon compound, such as a silicon oxide; and a lithium alloy containing at least one selected from the group consisting of tin, aluminum, zinc, and magnesium.
  • Examples of the carbon material include graphite (e.g., natural graphite, artificial graphite) and amorphous carbon.
  • the electrolyte may be a liquid electrolyte in which a solute, such as a lithium salt, is dissolved in a solvent.
  • the solvent may be a non-aqueous solvent, and may be water.
  • the electrolyte may be a solid electrolyte.
  • the electrolyte contains, for example, a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • the non-aqueous solvent include cyclic carbonic ester, chain carbonic ester, cyclic carboxylic acid ester, and chain carboxylic acid ester.
  • the lithium salt include LiPF 6 .
  • the separator is excellent in ion permeability and has moderate mechanical strength and electrically insulating properties.
  • the separator may be, for example, a microporous thin film, a woven fabric, or a nonwoven fabric.
  • the separator is preferably made of, for example, a polyolefin, such as polypropylene or polyethylene.
  • the secondary battery for example, has a structure in which an electrode group formed by winding the positive electrode and the negative electrode with the separator interposed therebetween is housed in an outer case, together with the electrolyte.
  • the wound-type electrode group may be replaced with a different form of electrode group, for example, a stacked-type electrode group formed by stacking the positive electrode and the negative electrode with the separator interposed therebetween.
  • the secondary battery may be in any form, such as cylindrical type, prismatic type, coin type, button type, or laminate type.
  • FIG. 1 is a partially cut-away schematic oblique view of a secondary battery including, as the positive electrode active material, a lithium-containing composite oxide obtained by the production method according to an embodiment of the present disclosure.
  • the battery includes a bottomed prismatic battery case 4, and an electrode group 1 and an electrolyte (not shown) housed in the battery case 4.
  • the electrode group 1 has a long negative electrode, a long positive electrode, and a separator interposed therebetween and preventing the positive and negative electrodes from directly contacting with each other.
  • the electrode group 1 is formed by winding the negative electrode, the positive electrode, and the separator around a flat plate-like winding core, and then removing the winding core.
  • a negative electrode lead 3 is attached at its one end to the negative electrode current collector of the negative electrode, by means of welding or the like.
  • the negative electrode lead 3 is electrically connected at its other end, via an electrically insulating plate (not shown) made of resin, to a negative electrode terminal 6 disposed at a sealing plate 5.
  • the negative electrode terminal 6 is electrically insulated from the sealing plate 5 by the resin gasket 7.
  • a positive electrode lead 2 is attached at its one end to the positive electrode current collector of the positive electrode, by means of welding or the like.
  • the positive electrode lead 2 is electrically connected at its other end, via the insulating plate, to the back side of the sealing plate 5. In other words, the positive electrode lead 2 is electrically connected to the battery case 4 serving as a positive electrode terminal.
  • the insulating plate separates the electrode group 1 from the sealing plate 5, and separates the negative electrode lead 3 from the battery case 4.
  • the sealing plate 5 is fitted at its periphery to the opening end of the battery case 4, and the fitted portion is laser-welded. In this way, the opening of the battery case 4 is sealed with the sealing plate 5.
  • the electrolyte injection hole provided in the sealing plate 5 is closed with a sealing stopper 8.
  • a lithium hydroxide monohydrate (average particle diameter (D50): 50 ⁇ m) was heated to dry at 150 °C for one hour, to prepare a lithium hydroxide (the first step).
  • Ni 0.85 Co 0.12 Al 0.03 (OH) 2 (average particle diameter (D50) of secondary particles: approx. 15 ⁇ m) was obtained as a hydroxide A by a coprecipitation technique.
  • the Ni 0.85 Co 0.12 Al 0.03 (OH) 2 was heated at 700°C in air for 2 hours, so that Ni 0.85 Co 0.12 Al 0.03 O was obtained as a composite oxide B (the second step).
  • the lithium hydroxide and the Ni 0.85 Co 0.12 Al 0.03 O were mixed together such that the atomic ratio: Li/(Ni+Co+Al) of Li to the total of Ni, Co and Al became 1.05/1, to give a mixture (the third step).
  • the mixture was compression-molded using a tableting machine, to give a columnar molded body (diameter: 6 mm, height: 6 mm) (the fourth step). At this time, the compression force was adjusted such that the density of the molded body became 1.6 g/cm 3 .
  • the mixing of the third step and the compression molding of the fourth step were each performed by a dry process.
  • the molded body was baked at 750 °C in an oxidizing atmosphere (oxygen concentration: 99%) for 5 hours, to give a baked body (lithium-containing composite oxide) (the fifth step).
  • the lithium-containing composite oxide had a composition represented by Li 1.05 Ni 0.85 Co 0.12 Al 0.03 O 2 .
  • the composition of the lithium-containing composite oxide was determined by ICP emission spectrometry.
  • the lithium hydroxide monohydrate was not heated to dry.
  • the second step was skipped.
  • the Ni 0.85 Co 0.12 Al 0.03 (OH) 2 obtained by a coprecipitation technique was used, in place of the Ni 0.85 Co 0.12 Al 0.03 O.
  • a lithium-containing composite oxide was obtained in the same manner as in Example 1, except the above.
  • the fourth step was skipped.
  • the mixture (powder) obtained in the third step was used, in place of the molded body.
  • a lithium-containing composite oxide was obtained in the same manner as in Example 1, except the above.
  • the lithium hydroxide monohydrate was not heated to dry.
  • the second step was skipped.
  • the Ni 0.85 Co 0.12 Al 0.03 (OH) 2 obtained by a coprecipitation technique was used, in place of the Ni 0.85 Co 0.12 Al 0.03 O.
  • the fourth step was skipped.
  • the mixture (powder) obtained in the third step was used, in place of the molded body.
  • a lithium-containing composite oxide was obtained in the same manner as in Example 1, except the above.
  • Example 1 In the lithium-containing composite oxide obtained in Example 1, the crystallite size was significantly increased, as compared to in the lithium-containing composite oxides obtained in Comparative Examples 1 to 3. In Example 1, the collapse of the molded body due to the generation of water during baking was suppressed. And the favorable contact between the lithium hydroxide and the composite oxide B and the high thermal conductivity of the molded body containing the both compounds were maintained. As a result, the reactivity between the two compounds was significantly improved, and the crystallinity of the baked body was significantly enhanced.
  • Comparative Example 1 water was produced from the molded body during baking, causing the molded body to collapse. And the thermal conductivity of the molded body decreased, and the lithium hydroxide and the composite oxide B failed to sufficiently contact with each other. As a result, the reactivity between the lithium hydroxide and the composite oxide B was degraded, and the crystallinity of the baked body was reduced.
  • Comparative Example 2 baking was conducted on the mixture (powder) which was poor in thermal conductivity. And the lithium hydroxide and the composite oxide B were not in sufficient contact with each other. As a result, the reactivity between the lithium hydroxide and the composite oxide B was degraded, and the crystallinity of the baked body was reduced.
  • Comparative Example 3 baking was conducted on the mixture (powder) which was poor in thermal conductivity. And the lithium hydroxide and the composite oxide A were not in sufficient contact with each other. As a result, the reactivity between the lithium hydroxide and the composite oxide A was degraded, and the crystallinity of the baked body was reduced.
  • the lithium-containing composite oxide obtained by the production method according to the present disclosure is suitably used, for example, as a positive electrode active material for a secondary battery required to have a high capacity and high reliability.
  • the secondary battery is preferably used, for example, as a main power source of a portable electronic device and the like, and as a power storage device (e.g., a device for storing natural energy, such as solar power).

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